CN104347871A - Nickel-hydrogen battery anode active material, preparation method thereof, anode containing anode active material and nickel-hydrogen battery - Google Patents

Nickel-hydrogen battery anode active material, preparation method thereof, anode containing anode active material and nickel-hydrogen battery Download PDF

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CN104347871A
CN104347871A CN201310319345.9A CN201310319345A CN104347871A CN 104347871 A CN104347871 A CN 104347871A CN 201310319345 A CN201310319345 A CN 201310319345A CN 104347871 A CN104347871 A CN 104347871A
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hydrogen
nickel
negative pole
active material
powder
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耿伟贤
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BYD Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/30—Nickel accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/242—Hydrogen storage electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/383—Hydrogen absorbing alloys
    • H01M4/385—Hydrogen absorbing alloys of the type LaNi5
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

A provided nickel-hydrogen battery anode active material comprises a hydrogen-storing alloy powder and an additive powder, and the additive powder is a porous alloy powder formed by a first metal element, a second metal element and zinc, wherein the first metal element is at least one of gadolinium, erbium and samarium, and the second metal element is at least one of nickel and cobalt. The invention also provides a preparation method of the negative active material, an anode containing the negative active material and a nickel-hydrogen battery containing the anode. The negative active material is capable of reducing the internal voltage of the nickel-hydrogen battery and further improving the cycle life of the battery.

Description

A kind of nickel-hydrogen battery negative pole active material and preparation method thereof and containing the negative pole of this negative active core-shell material and Ni-MH battery
Technical field
The invention belongs to Ni-MH battery field, particularly relate to a kind of nickel-hydrogen battery negative pole active material and preparation method thereof and containing the negative pole of this negative active core-shell material and Ni-MH battery.
Background technology
Ni-MH battery has that specific energy is high, the pollution without cadmium, the advantage such as environmentally friendly.But Ni-MH battery constantly carries out along with charge and discharge cycles, the oxidation resistance of the hydrogen-storage alloy powder of composition nickel-hydrogen battery negative pole also constantly declines, especially the oxygen that during battery overcharge, positive pole is separated out, can hydrogen-storage alloy be impelled further to be oxidized, cause the decline of the actual hydrogen storage capacity of hydrogen-storage alloy negative pole, namely hydrogen-storage alloy negative pole charging ability declines, and when battery can be caused so again to charge, internal hydrogen dividing potential drop rises, thus causes inner pressure of battery to rise.Inner pressure of battery is elevated to a certain degree, and battery safety valve can be made to open, and while gas is released, electrolyte also can overflow, and causes electrolyte solution loss, and the internal resistance of cell increases.Thus along with the carrying out of charge and discharge cycles, discharge capacity of the cell constantly declines, final shorter battery life.
Japanese Unexamined Patent Publication JP6-215765 discloses a kind of alkaline battery, this alkaline battery comprises the positive pole formed primarily of metal oxide, the negative pole, barrier film and the alkaline electrolyte that form primarily of hydrogen-bearing alloy powder, wherein, described negative pole comprises hydrogen-bearing alloy powder and is selected from by Y, Y 2o 3, Y (OH) 3and Y 2(SO 4) 3or the material containing arbitrarily yttrium of the group of their mixture composition, make the surface-coated this material of hydrogen bearing alloy.Hydrogen bearing alloy is oxidized by the oxygen produced by positive pole when can solve overcharge by this technical scheme, thus makes the internal resistance rising of battery, the problem of charge-discharge performance variation.
But such scheme only can solve the problem that the oxidation resistance of hydrogen bearing alloy own reduces.Because Ni-MH battery is in charging process, there is the side reaction of liberation of hydrogen in negative pole, simultaneously battery positive pole precipitated oxygen when overcharging.Although capacity of negative plates is higher than positive electrode capacity during design Ni-MH battery, because hydrogen storage alloy negative hydrogen oxygen recombination speed is comparatively slow, still can makes the hydrogen of generation, carrier of oxygen accumulates at inside battery, cause inner pressure of battery to rise.When inner pressure of battery is elevated to a certain degree, battery safety valve still can be opened, and electrolyte overflows with gas, and the amount of electrolyte is reduced, and internal resistance increases, and discharge capacity of the cell declines, and finally causes battery cycle life to shorten.Therefore, in such scheme, the cycle life of battery still has much room for improvement.
Summary of the invention
The present invention is the technical problem that oxidation resistance is poor, cycle life is short solving negative pole in existing Ni-MH battery, provides that a kind of oxidation resistance is strong, the nickel-hydrogen battery negative pole active material that has extended cycle life and preparation method thereof and contain negative pole and the Ni-MH battery of this negative active core-shell material.
The invention provides a kind of nickel-hydrogen battery negative pole active material, this negative active core-shell material contains hydrogen-storage alloy powder and additive powder; Described additive powder is the porous alloy powder that the first metallic element, the second metallic element and zinc are formed; Described first metallic element is at least one element in gadolinium, erbium and samarium, and described second metallic element is at least one element in nickel and cobalt.Present invention also offers a kind of preparation method of nickel-hydrogen battery negative pole active material, the method comprises and being mixed with additive powder by hydrogen-storage alloy powder, and described additive powder is the porous alloy powder that the first metallic element, the second metallic element and zinc are formed; Described first metallic element is at least one element in gadolinium, erbium and samarium, and described second metallic element is at least one element in nickel and cobalt.
Present invention also offers a kind of nickel-hydrogen battery negative pole, this negative pole comprises active material, binding agent, thickener and deionized water; Wherein said active material is nickel-hydrogen battery negative pole active material of the present invention.
Present invention also offers a kind of Ni-MH battery, comprise battery container, electrode group and electrolyte, electrode group and electrolyte are sealed in battery container, and electrode group comprises winding or stacked positive pole, barrier film and negative pole successively, and described negative pole is nickel-hydrogen battery negative pole of the present invention.
Present invention employs the method for the alloy powder adding the porous surface be made up of two metalloid elements and a small amount of zinc in nickel-hydrogen battery negative pole active material.Wherein the first metallic element is at least one element in gadolinium, erbium and samarium, and the second metallic element is at least one element in nickel and cobalt.Described additive powder be the alloy powder that formed of the first metallic element and the second metallic element and metallic zinc after high temperature alkali dipping, remove portion metallic zinc and the alloy powder of porous surface that formed.Additive powder is dispersed between described hydrogen-storage alloy powder particle, also has portions additive powder adsorption at described hydrogen-storage alloy powder particle surface.
For cobalt and nickel, because cobalt and nickel element can be slightly soluble in electrolyte, can be reduced to again cobalt and the nickel of metallic state in battery charging process, separate out on hydrogen-storage alloy surface, not molten cobalt and nickel then still stay hydrogen-storage alloy surface.Cobalt and nickel element are dissolved in electrolyte, cobalt and the whole process of nickel precipitation on hydrogen-storage alloy surface of metallic state is reduced to again in battery charging process, along with charge and discharge cycles is slowly carried out gradually, the hydrogen-storage alloy unsalted surface thus produced along with charge and discharge cycles also can separate out the cobalt and nickel that there are metallic state; And metal gadolinium, erbium and samarium element are in the periodic table of chemical element, belong to lanthanides, nature is comparatively active, and oxidizable is Gd 2o 3, Er 2o 3, Sm 2o 3or Gd (OH) 3, Er (OH) 3, Sm (OH) 3but because metal gadolinium, erbium and samarium element exist with alloy form with as the cobalt of the second metallic element and nickel element, therefore this process is also slowly carried out gradually along with charge and discharge cycles, the hydrogen-storage alloy unsalted surface thus produced along with charge and discharge cycles also can separate out Gd 2o 3, Er 2o 3, Sm 2o 3or Gd (OH) 3, Er (OH) 3, Sm (OH) 3.
But because metal gadolinium, erbium and samarium element exist with alloy form with as the cobalt of the second metallic element and nickel element; therefore the oxidation that metal gadolinium, erbium and samarium element produce with charge and discharge cycles is too slow; can not be adequately protected the hydrogen-storage alloy unsalted surface produced with charge and discharge cycles, namely fully can not separate out Gd at hydrogen-storage alloy unsalted surface 2o 3, Er 2o 3, Sm 2o 3or Gd (OH) 3, Er (OH) 3, Sm (OH) 3.Simultaneously, cobalt and nickel element are dissolved in electrolyte, in battery charging process, be reduced to again cobalt and the whole process of nickel precipitation on hydrogen-storage alloy surface of metallic state, also too slow, the hydrogen-storage alloy unsalted surface thus produced with charge and discharge cycles fully can not separate out the cobalt and nickel that there are metallic state.Namely can not solve the technical problem that oxidation resistance is poor, cycle life is short of negative pole in existing Ni-MH battery at all,
The present inventor is through repetition test, it is unexpected that discovery additive powder be that the alloy powder of the first metallic element and the second metallic element and metallic zinc formation is after high temperature alkali dipping, remove most of metallic zinc and the alloy powder of the porous surface formed time, the technical problem that oxidation resistance is poor, cycle life is short of negative pole in existing Ni-MH battery can be solved at all.
Additive powder is due to porous surface, therefore additive powder surface area increases greatly, the contact area of additive powder and alkali lye also greatly increases, greatly facilitate cobalt and nickel element dissolving in the electrolytic solution, thus cobalt and nickel element are dissolved in electrolyte, cobalt and the whole process of nickel precipitation on hydrogen-storage alloy surface of metallic state is reduced to again in battery charging process, can carry out very abundant along with charge and discharge cycles, the hydrogen-storage alloy unsalted surface thus produced with charge and discharge cycles can separate out cobalt and the nickel of fully enough metallic states.Additive powder porous surface simultaneously; also the oxidation problem too slowly that metal gadolinium, erbium and samarium element produce with charge and discharge cycles can be solved; thus can adequately protect the hydrogen-storage alloy unsalted surface produced along with charge and discharge cycles, fully separated out Gd at hydrogen-storage alloy unsalted surface 2o 3, Er 2o 3, Sm 2o 3or Gd (OH) 3, Er (OH) 3, Sm (OH) 3.Like this along with charge and discharge cycles is carried out gradually, on hydrogen-storage alloy surface, especially fully form the oxide of gadolinium, erbium and samarium or the superpacket coating of hydroxide and metallic cobalt or nickel at the hydrogen-storage alloy unsalted surface produced along with charge and discharge cycles.In superpacket coating, the oxide of gadolinium, erbium and samarium or hydroxide can improve the oxidation resistance of hydrogen-storage alloy itself; Metallic cobalt and nickel then have hydrogen oxygen recombination catalytic capability, and can improve the oxygen ability that disappears of hydrogen-storage alloy itself, improve inner pressure of battery, thus the inventive method really can improve the cycle life of Ni-MH battery.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The invention provides a kind of nickel-hydrogen battery negative pole active material, this negative active core-shell material contains hydrogen-storage alloy powder and additive powder; First metallic element described in the porous alloy powder that described additive powder is the first metallic element, the second metallic element and zinc are formed is at least one element in gadolinium, erbium and samarium, and described second metallic element is at least one element in nickel and cobalt.
In order to the cycle life of the oxidation resistance and Ni-MH battery that better improve negative active core-shell material, preferably, with the total weight of negative active core-shell material for benchmark, the content of described additive powder is 1-10wt%.
In order to the cycle life of the oxidation resistance and Ni-MH battery that better improve negative active core-shell material, preferably, with the total weight of additive powder for benchmark, the content of described first metallic element is 10-90wt%, the content of described second metallic element is 10-90wt%, and the content of described zinc is 0.01-1.00wt%.
In the present invention, preferably, the porosity of described porous alloy powder is 8-25%.Porosity is alloyed powder within the scope of this, more effectively can facilitate cobalt and nickel element dissolving in the electrolytic solution.In the present invention, preferably, the average grain diameter of described hydrogen-storage alloy is 35-65 μm, and the average grain diameter of described additive powder is 0.1-20 μm, and the average grain diameter of described additive powder is more preferably 0.2-10 μm.The average grain diameter of additive powder, at 0.1-20 μm, can make more additive powder be adsorbed on the surface of hydrogen-storage alloy, makes the performance of hydrogen-storage alloy better.And the average grain diameter of described additive powder is greater than 20 μm, then manifold additive powder is scattered between described hydrogen-storage alloy powder particle, be difficult to be adsorbed in described hydrogen-storage alloy powder surface, additive powder particle is too large in addition, also be unfavorable for the stripping of the first metallic element and the second metallic element, thus can affect the performance of hydrogen-storage alloy; The average grain diameter of additive powder is less than 0.1 μm, then increase powder difficulty of processing, and processing cost increases.
In the present invention, described hydrogen-storage alloy has no particular limits, and the various hydrogen-storage alloys can commonly used for this area, as AB 5type RE-Ni hydrogen storage, La-Mg-Ni cording have PuNi 3the AB of type structure 3type hydrogen-storage alloy and La-Mg-Ni cording have Ce 2ni 7the A of type structure 2b 7type hydrogen-storage alloy.
Present invention also offers a kind of preparation method of nickel-hydrogen battery negative pole active material, the method comprises and being mixed with additive powder by hydrogen-storage alloy powder, and described additive powder is the porous alloy powder that the first metallic element, the second metallic element and zinc are formed; Described first metallic element is at least one element in gadolinium, erbium and samarium, and described second metallic element is at least one element in nickel and cobalt.
In order to the cycle life of the oxidation resistance and Ni-MH battery that better improve negative active core-shell material, preferably, with the total weight of negative active core-shell material for benchmark, the content of described additive powder is 1-10wt%.
In order to the cycle life of the oxidation resistance and Ni-MH battery that better improve negative active core-shell material, preferably, with the total weight of additive powder for benchmark, the content of described first metallic element is 10-90wt%, the content of described second metallic element is 10-90wt%, and the content of described zinc is 0.01-1.00wt%.
In the present invention, described additive powder be the alloy powder that formed of the first metallic element, the second metallic element and metallic zinc after high temperature alkali dipping, remove portion metallic zinc and the porous alloy powder that formed.Described high temperature alkali refers to and alkali lye is heated to the 80-100 DEG C of solution obtained.
Preferably, the average grain diameter of described hydrogen-storage alloy is 35-65 μm, and the average grain diameter of described additive powder is 0.1-20 μm, the average grain diameter more preferably 0.2-10 μm of described additive powder.
In the present invention, described hydrogen-storage alloy has no particular limits, and the various hydrogen-storage alloys can commonly used for this area, as AB 5type RE-Ni hydrogen storage, La-Mg-Ni cording have PuNi 3the AB of type structure 3type hydrogen-storage alloy and La-Mg-Ni cording have Ce 2ni 7the A of type structure 2b 7type hydrogen-storage alloy.
Present invention also offers a kind of nickel-hydrogen battery negative pole, this negative pole comprises active material, binding agent, thickener and deionized water; Wherein said active material is nickel-hydrogen battery negative pole active material of the present invention.
Present invention also offers a kind of Ni-MH battery, comprise battery container, electrode group and electrolyte, electrode group and electrolyte are sealed in battery container, and electrode group comprises winding or stacked positive pole, barrier film and negative pole successively, and described negative pole is nickel-hydrogen battery negative pole of the present invention.
In the present invention, when the oxide of gadolinium, erbium and samarium or hydroxide are overlayed on hydrogen-storage alloy surface, the oxidation resistance of hydrogen-storage alloy itself can be improved; Metallic cobalt and nickel then have hydrogen oxygen recombination catalytic capability, and can improve the oxygen ability that disappears of hydrogen-storage alloy itself, improve inner pressure of battery, thus the inventive method really can improve the cycle life of Ni-MH battery.
Below by specific embodiment, the present invention is described in detail.
Embodiment 1
< porous alloy powder makes >: by Gd, Co and Zn tri-kinds of raw metals are after 26.8: 62.2: 11 batchings, be cast into alloy pig through vacuum induction melting furnace melting, the alloyed powder that average grain diameter is 1.6 μm is formed through pulverizing, then to be impregnated in temperature be 90 DEG C of concentration is stir 60min in the KOH strong base solution of 8mol/L, to remove most of zinc, finally obtain average grain diameter be 1.5 μm containing Gd be 30wt%, the content of zinc is only 0.50wt%, all the other are the alloy powder of the Gd-Co-Zn porous surface of cobalt, the porosity of alloyed powder is 16.1%.
< hydrogen-storage alloy negative pole makes >: be made up by vacuum induction melting of cerium-rich mischmetal Mm and Ni, Co, Mn, Al, consist of MmNi 3.55co 0.75mn 0.4al 0.3mmNi 5in series hydrogen storage alloy, add above-mentioned porous alloy powder 2wt%, and add appropriate binding agent PTFE, thickener HPMC and deionized water, mixing and stirring, is mixed with slurry, and slurry makes negative plate.
< nickel metal hydride secondary battery makes >: positive plate, the barrier film combine volume of the above-mentioned hydrogen-storage alloy negative plate made and the spherical nickel hydroxide containing solid solution Co, Zn and conductive auxiliary agent cobalt or cobalt compound are coiled into electrode group, insert in AA shaped steel shell, seal after injecting the electrolyte based on potassium hydroxide of proportion 1.30, make the AA type nickel metal hydride secondary battery A1 that capacity specifications is 1800mAh.
Embodiment 2
Ni-MH battery A2 is prepared according to the method for embodiment 1.Difference is: to add average grain diameter in hydrogen-storage alloy be 1.5 μm be 30wt%, Er is 20wt% containing Gd, and zinc is 0.34wt%, and all the other are the alloy powder 1wt% of the Gd-Er-Ni-Zn porous surface of Ni, and the porosity of alloyed powder is 19.4%.
Embodiment 3
Ni-MH battery A3 is prepared according to the method for embodiment 1.Difference is: add in hydrogen-storage alloy average grain diameter be 1.5 μm containing Gd be 60wt%, Ni be 30wt%, zinc is 1.0wt%, all the other are the alloyed powder 10wt% of the Gd-Ni-Co-Zn porous surface of Co, and the porosity of alloyed powder is 8%.
Embodiment 4
Ni-MH battery A4 is prepared according to the method for embodiment 1.Difference is: add in hydrogen-storage alloy average grain diameter be 1.5 μm containing Er be 10wt%, zinc is 0.19wt%, and all the other are the alloy powder 5wt% of the Er-Co-Zn porous surface of Co, and the porosity of alloyed powder is 21.4%.
Embodiment 5
Ni-MH battery A5 is prepared according to the method for embodiment 1.Difference is: add in hydrogen-storage alloy average grain diameter be 1.5 μm containing Sm be 90wt%, zinc is 0.13wt%, and all the other are the alloy powder 8wt% of the Sm-Co-Zn porous surface of Co, and the porosity of alloyed powder is 22.5%.
Embodiment 6
Ni-MH battery A6 is prepared according to the method for embodiment 1.Difference is: add in hydrogen-storage alloy negative pole average grain diameter be 1.5 μm containing Gd be 30wt%, zinc is 0.61wt%, and all the other are the alloy powder of the Gd-Co-Zn porous surface of cobalt is 0.5wt%, and the porosity of alloyed powder is 14.3%.
Embodiment 7
Ni-MH battery A7 is prepared according to the method for embodiment 1.Difference is: add in hydrogen-storage alloy negative pole average grain diameter be 1.5 μm containing Gd be 30wt%, zinc is 0.01wt%, and all the other are the alloy powder of the Gd-Co-Zn porous surface of cobalt is 4.0wt%, and the porosity of alloyed powder is 25%.
Embodiment 8
Ni-MH battery A8 is prepared according to the method for embodiment 1.Difference is: add in hydrogen-storage alloy negative pole average grain diameter be 1.5 μm containing Gd be 30wt%, zinc is 0.68wt%, and all the other are the alloy powder of the Gd-Co-Zn porous surface of cobalt is 7.0wt%, and the porosity of alloyed powder is 13.2%.
Embodiment 9
Ni-MH battery A9 is prepared according to the method for embodiment 1.Difference is: add in hydrogen-storage alloy negative pole average grain diameter be 1.5 μm containing Gd be 30wt%, zinc is 0.84wt%, and all the other are the alloy powder of the Gd-Co-Zn porous surface of cobalt is 12wt%, and the porosity of alloyed powder is 10.9%.
Comparative example 1
Ni-MH battery CA1 is prepared according to the method for embodiment 1.Difference is: do not add alloy powder in hydrogen-storage alloy.
Comparative example 2
Ni-MH battery CA2 is prepared according to the method for embodiment 1.Difference is: add in hydrogen-storage alloy average grain diameter be 1.5 μm containing Gd 2o 3powder 2wt%.
Comparative example 3
Ni-MH battery CA1 is prepared according to the method for embodiment 1.Difference is: add in hydrogen-storage alloy average grain diameter be 1.5 μm containing Er 2o 3powder 2wt%.
Comparative example 4
Ni-MH battery CA1 is prepared according to the method for embodiment 1.Difference is: add in hydrogen-storage alloy average grain diameter be 1.5 μm containing Sm 2o 3powder 2wt%.
Method of testing and data
1, inner pressure of battery measures: by the battery CA1-CA4 of the battery A1-A9 in embodiment and comparative example after first discharge and recharge activation, to measure inner pressure of battery during 1C (1800mA) current charges 120min.Inner pressure of battery measures by loading onto manometric method bottom battery steel shell, and its result is as table 1.
2, battery cycle life measures: by the battery CA1-CA4 of the battery A1-A9 in embodiment and comparative example after first discharge and recharge activation, with 0.2C (360mA) current charges 7.5 hours, and be aided with-Δ V=10mV controls; simultaneously it is 1.0V that 1C is discharged to cell voltage, each charge or discharge terminate all to shelve 15min afterwards, cycle-index when discharge capacity of the cell is down to 70% of initial stage constant, is cycle life.Its result is as table 1.
Table 1
Battery Cathode additive agent kind Inner pressure of battery (atm) Cycle life (secondary)
A1 Gd-Co 5.2 680
A2 Gd-Er-Ni 7.0 670
A3 Gd-Ni-Co 4.3 682
A4 Er-Co 4.8 663
A5 Sm-Co 4.5 679
A6 Gd-Co 13.6 589
A7 Gd-Co 4.9 681
A8 Gd-Co 4.6 685
A9 Gd-Co 4.5 650
CA1 Without adding 22.0 319
CA2 Gd2O3 22.9 430
CA3 Er2O3 21.2 435
CA4 Sm2O3 23.5 421
As can be seen from Table 1, the interior pressure of the Ni-MH battery A1-A9 of the embodiment of the present invention is significantly less than the Ni-MH battery CA1-CA4 in comparative example, and cycle life is also obviously better than the Ni-MH battery CA1-CA4 in contrast.Negative active core-shell material of the present invention is described, the interior pressure of Ni-MH battery can be reduced, and battery cycle life is improved further.Meanwhile, when the alloy powder addition of porous surface is less than 1.0wt%, large when inner pressure of battery is greater than 1.0wt% than alloy powder addition.When the alloy powder addition of porous surface is at more than 1.0wt%, inner pressure of battery and cycle life are all greatly improved, but to improve degree extremely limited for inner pressure of battery and cycle life when the alloy powder addition of porous surface is 10wt%, and addition increases further and can increase the cost of raw material, therefore alloy powder addition controls in 1-10.0wt% better effects if.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.

Claims (16)

1. a nickel-hydrogen battery negative pole active material, is characterized in that, this negative active core-shell material contains hydrogen-storage alloy powder and additive powder; Described additive powder is the porous alloy powder that the first metallic element, the second metallic element and zinc are formed; Described first metallic element is at least one element in gadolinium, erbium and samarium, and described second metallic element is at least one element in nickel and cobalt.
2. nickel-hydrogen battery negative pole active material according to claim 1, is characterized in that, with the total weight of negative active core-shell material for benchmark, the content of described additive powder is 1-10wt%.
3. nickel-hydrogen battery negative pole active material according to claim 1, it is characterized in that, with the total weight of additive powder for benchmark, the content of described first metallic element is 10-90wt%, the content of described second metallic element is 10-90wt%, and the content of described zinc is 0.01-1.00wt%.
4. nickel-hydrogen battery negative pole active material according to claim 1, is characterized in that, the porosity of described porous alloy powder is 8-25%.
5. nickel-hydrogen battery negative pole active material according to claim 1, is characterized in that, the average grain diameter of described hydrogen-storage alloy is 35-65 μm, and the average grain diameter of described additive powder is 0.1-20 μm.
6. nickel-hydrogen battery negative pole active material according to claim 5, is characterized in that, the average grain diameter of described additive powder is 0.2-10 μm.
7. nickel-hydrogen battery negative pole active material according to claim 1, is characterized in that, described hydrogen-storage alloy is AB 5type RE-Ni hydrogen storage, La-Mg-Ni cording have PuNi 3the AB of type structure 3type hydrogen-storage alloy and La-Mg-Ni cording have Ce 2ni 7the A of type structure 2b 7type hydrogen-storage alloy.
8. a preparation method for nickel-hydrogen battery negative pole active material, is characterized in that, the method comprises and being mixed with additive powder by hydrogen-storage alloy powder, and described additive powder is the porous alloy powder that the first metallic element, the second metallic element and zinc are formed; Described first metallic element is at least one element in gadolinium, erbium and samarium, and described second metallic element is at least one element in nickel and cobalt.
9. the preparation method of nickel-hydrogen battery negative pole active material according to claim 8, is characterized in that, with the total weight of negative active core-shell material for benchmark, the content of described additive powder is 1-10wt%.
10. the preparation method of nickel-hydrogen battery negative pole active material according to claim 5, it is characterized in that, with the total weight of additive powder for benchmark, the content of described first metallic element is 10-90wt%, the content of described second metallic element is 10-90wt%, and the content of described zinc is 0.01-1.00wt%.
The preparation method of 11. nickel-hydrogen battery negative pole active materials according to claim 8, it is characterized in that, described additive powder be the alloy powder that formed of the first metallic element, the second metallic element and metallic zinc after high temperature alkali dipping, remove portion metallic zinc and the porous alloy powder that formed.
The preparation method of 12. nickel-hydrogen battery negative pole active materials according to claim 8, is characterized in that, the average grain diameter of described hydrogen-storage alloy is 35-65 μm, and the average grain diameter of described additive powder is 0.1-20 μm.
The preparation method of 13. nickel-hydrogen battery negative pole active materials according to claim 12, is characterized in that, the average grain diameter of described additive powder is 0.2-10 μm.
The preparation method of 14. nickel-hydrogen battery negative pole active materials according to claim 8, is characterized in that, described hydrogen-storage alloy is AB 5type RE-Ni hydrogen storage, La-Mg-Ni cording have PuNi 3the AB of type structure 3type hydrogen-storage alloy and La-Mg-Ni cording have Ce 2ni 7the A of type structure 2b 7type hydrogen-storage alloy.
15. 1 kinds of nickel-hydrogen battery negative poles, is characterized in that, this negative pole comprises active material, binding agent, thickener and deionized water; Wherein said active material is the nickel-hydrogen battery negative pole active material described in claim 1-7 any one.
16. 1 kinds of Ni-MH batteries, comprise battery container, electrode group and electrolyte, electrode group and electrolyte are sealed in battery container, and electrode group comprises winding or stacked positive pole, barrier film and negative pole successively, it is characterized in that, described negative pole is nickel-hydrogen battery negative pole according to claim 15.
CN201310319345.9A 2013-07-26 2013-07-26 Nickel-hydrogen battery anode active material, preparation method thereof, anode containing anode active material and nickel-hydrogen battery Pending CN104347871A (en)

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